Dyestuffs containing metal and process of making same



Patented Mar. 29, 71932 a I unr se, states FRITZ srnA UB, oF- imsnn,HERMANN soIINEfDEm' or" simian, Niles nAsnn Ai in HAN-s YER,- or 'BAsEL,SWITZERLAND, AssreNon To DUSTRY IN BASLE, or BASEL, SWITZERLAN vDYESTUFFS CONTAINING METAL AND PROCESS or MAKING sAME.

No Drawing. Application filed. September 12, September The presentinvention relates to the inanuv facture of dyestuffs containing metal.It

terial dyed with the new dyestuffs.

comprises the process of making these. dye-' stuffs, thedyestuffs-themselves, and'the ma- Hitherto it has often not beenpossible to convert ortho-hydroXy azo-dyestuffs in a smooth manner intotheir complexmetal compounds by treating the said dyestuffs in an"alkaline medium with such hydroxides of pound containing hydro'ziylgroups and a hydroxide of a metal which is capable of forming complexmetal compounds, which hydroXi-des are insoluble in caustic alkali, ithaving been found that these .inetal compounds are particularly suitablefor introducing these metals into the molecule of a dyestuff. r

Such organic compounds containing hydroxyl groups are, for examplepolyhydrie alcohols, or phenols, tanninmsaccharides, derivatives ofcellulose, lignines, and the like, and hydroxides of metals, whichcomeinto consideration are inter alia those of copper,

iron, cobalt, nickel, manganese, titanium, and -"so on. With the aid ofthese products the reaction proceeds much more smoothly than with thesimple hydroxides which are not soluble, and the manufacture of the newprod note is conducted in a simple manner by heating the dyestuff with asolution or suspension of the metal compound. V

The dyestuffs containing metal obtainable in accordance with theinvention are different from and superior to the dyestuffscontaingzslsefial $91 and in. Switzerland 2 1927. A

re t! SOCIETY: on CHEMICAL 1m;

ing the same metal but made by other pro- The invention is applicable tothe production of simple metal compounds of mono-' asodyestuifs or ofpoly-azo-dyestuffs, and to the productlon of mixed metal compounds ofsuch dyestuffs, containing more than one metal (compare specificationsSerial No.

801,165,and'305,135).

The following ex amples illustrate thei-n ventionthe parts being byweight.

EmampZQL Qi-Q parts of crystallized copif form of blue copperhydroxide-hydrate at ordinary temperature by the'addition of a.slightexcess of a solution of caustic soda.

j per sulphate are dissolved in. 500' parts of water and the copper isprecipitated in the The precipitate is-filteredand washed andthendissolved inv a mixture-of? 5 parts of water, 25 parts of potassiumhydroxide andr8 partsof glycerine (com-pare Gmelin-Kraut, Handbuch deranorgan. Ghem'ie, 7th Edition, 1

Volume V, p. 7 7 5 et. seq). 7

12.77 parts of the dyestuff from diazotized l 5-nitro2-aminosl-phenloland ortho-anisyl- 2 amino 5 hydroXyna-phthalene-Z-sulfonic acid of theformula v V OCH:

are dissolved 500 parts of: water with the addition of 3parts of causticpotash. The

l's o solution so obtained is mixed with parts ofvthe solutioncontaining copper prepared 1y by neutralizing the solution, separated byfiltration and washed. When dried it is a dark brown powder having abronze lustre; it is soluble in hot water to a pure blue solution. Thedyestuif dyes cotton in a neutral bath reddish blue shades of very goodfastness to light. 7,

Example 2-13 parts of cobaltous Chloride are dissolved in 200 parts ofwater and the solution is mixed with parts of glycerine. There are thenadded successively a solution of parts of caustic potash in l5 parts of"water, and 55 partsof a dyestuif paste of 43% I strength (l/QOthmolecular proportion) of the dyestufi' from diazotized 2-amino-1-hydroxy-naphthalene-t: S-disulphonic acid, and fl-naphthol of the formula1 r on on After boiling the mixture for 6 hours in a reflux apparatus,there is-added a solution of parts of caustic potash in 25 parts ofwater, and the whole is boiled for a further 15 hours, after which it isdiluted to 500 parts,

'filtered, neutralized by addition of acetic acid, and salted out. Thecobalt compound of the dyestuif which is thus precipitated incrystalline form is, when dried, a brown violet powder having a faintlybronze appearance; it dissolves in water and in caustic soda lye of 10per cent strength to a violet solution, and in concentrated sulphuricacid to ablue violet solution. In an acetic acid' bath it dyes wool andsilk in red violet shades of good fastness.

In a similar manner one proceeds with I other azo-dyestufis and thederivatives soluble in alkali which the polyhydric alcohols, or phenols,tannins, saccharides, derlvatives of cellulose, .hgnmes, and so on,yield with the hydroxides of iron, manganese, titanium, A

and so on.

What we claim is 1. A manufacture of azo-dyestufis containing metal bytreatingortho hydroxy-azo-dye stuffs with a metal compound obtainable byreaction, in presence of a caustic alkali, between a polyhydric alcoholand a hydroxide of a metal having an atomic weight between 59 and 64.

2. A manufacture of aZo-dyestuifs containing metal by treatingortho-hydroXy-azo-dyestuffs with a metal compound obtainable byreaction, in presence of a caustic alkali, be tween glycerine, and ahydroxide of copper.

3. As new products the aZo-dyestuffs containing such metals thehydroxides of which are insoluble in caustic alkalies, which productsare obtained by treating ortho-hydroXyazo-dyestufl's with a metalcompound obtain-

